Yarn treating processes and compositions therefor



Patented Apr. 4, 1939 PATENT OFFICE YARN TREATING PROCESSES AND COMPU-SITIONS THEREFOR Joseph B. Dickey and James G. McNally, Rochester, N.Y., assignors o Eastman Kodak Company, Rochester, N. Y., a corporationof New Jersey No Drawing. Application November 26, 1937, Serial No.176,682

22 Claims.

This invention relates to theconditioning of textile yarns and moreparticularly to the conditioning of filaments and yarns composed oforanic derivatives of cellulose such as cellulose acetate, celluloseacetate propionate, cellulose acetate butyrate, etc., to render themmore amenable to textile operations'such as knitting and the like.

As is well known in the manufacture of yarns, particularly thosecomposed of or containing cellulose organic derivatives, it is necessaryto treat the yarn in order to reduce the tendency toward breakage of theindividual filaments or fibers when they are subjected, to variousmechanical strains and to lubricate the yarn in order to facilitatehandling in such operations as spinning, twisting, winding and reeling.It is also necessary to treat yarn to adapt it for use as warp orfilling or for the manufacture of various types of knitted fabrics. Inknitting, it is particularly important that the yarn be soft and pliablein order that it may conform readily to the contour of the needles andthus produce a closely knit fabric free from such defects as stitchdistortion, pin holes, laddering, and the like.

Heretofore it has been proposed to employ softening agents such aspolyhydric alcohols and similar agents as ingredients of yarnconditioning or lubricating formulas, generally in connec tion withmineral, animal or vegetable oils. It hasbeen found, however, that mostof the known softening agents and the various formulas containing themhave certain drawbacks, one of the most serious of which is high vaporpressure, and in some cases too drastic a solvent action on the yarn.Many of such agents possess slight or in-' suficient solvent power forthe lubricantswith which they are used, and it is accordingly necessaryto employ blending agents or, emulsifying agents in order to obtainoperable yarn treating formulas. 'In addition, many of the knownsoftening and lubricating agents are insufiiciently soluble in water topermit satisfactory removal by aqueous scour baths? This invention hasas its principal object to provide an entirely new class of yarnconditioning agents which are particularly adapted for the treatment ofyarn composed of or containing oranic derivatives of cellulose andcapable of lubricating, softening and rendering such yarns more amenableto knitting and other textile operations. A further and specific objectis to provide a class of conditioning agents which augment or assist thelubricating action of various lubricants when applied to such yarns. Astill further object is to provide yarn softening and lubricatingformulaswhich can be readily removed from the yarns by the usual scourbaths. A still furtherobject is to provide an improved method for theconditioning of yams, particularly those composed of or containingorganic derivatives of cell whereby the yarn is rendered soft andpliable and capable of employment in a variety of textile operationswhere complicated designs or stitches are employed. Still another objectis to provide new chemical compounds having the structure and propertiesdiscussed below. .Another object is to provide an improved type of yarnwhich is especially amenable to textile operations including knitting,weaving, spinning, and the like. Other objects will appear hereinafter.

These objects are accomplished by the following invention which in itsbroader aspects comprises the discovery that acetals having the generalformulas:

and

where R and R may be hydrogen, alkoxy or alkyl and tetrahydrofurfurylgroups, may be used as yarn conditioning agents and particularly as osesuch as cellulose acetate,

softening agents, with or without the addition of animal, mineral, orvegetable oils, in the treatment of yarns composed of or containingorganic derivatives of cellulose. We have found that these compoundshave a' slight solvent and/or softening action on cellulose organicderivative yarns which renders-such yarns soft and pliable without atthe same time having too drastic a' solvent action thereon.

In accordance with the invention these compounds may be applied directlyto the yarn during or after spinning, or may be added to the spinningsolution-itself. We have found that these compounds have exceptionalsolvent powers which enable them to dissolve mineral oils and blown andunblown, drying and semi-drying, vegetable and animal oils andaccordingly they may be, and preferably are, employed as ingredients ofyarn conditioning or lubricating formulas in conjunction with agentswhich function wholly or partially as lubricants.

In the following examples and description we have set forth several ofthe preferred embodiments of our invention, but they are included merelyfor purposes of illustration and not as a limitation thereof. i

The compounds which we have found particularly valuable for treatingyarn in accordance with the process herein described may be prepared inaccordance with the general methods outlined in the literature asfollows:

Preparation of acetals using acetylene and alcohols Nieuwlands,'J. Amer.Chem. Soc. 45, 1552 Furfural cyclic acetals -U. 8. Pat. 1,934,309Hyrogenation of furfural acetals -Minnie and Adkins, J. Amer. Chem. Soc.55,

-Adkins, ibid., 54, 1651 (1932) In order to illustrate the preparationof compounds in accordance with our invention, the following examplesare given:

Preparation of One gram of red meruric oxide is partially dissolved bygentle warming in grams of 50% boron trifiuoride in methanol.Tetrahydrofurfuryl alcohol (102 grams; 1 mol) isthen added, the flaskplaced in cold water, and the mixture treated with dry acetylene untilthe theortical quantity is absorbed (13 grams). The flask and contentsare shaken frequently during the addition. A further 1 gram of HgO isadded as the reaction becomes slow.

Preparation of tetrahydrofurfural glycol Five hundred sixty four grams(4 mols) furfural glycol, 5 grams isoamylamine, and 20 gramsRa'neycatalyst are treated with hydrogen at 150 under 1500 poundspressure for 20 hours. The product is worked up by known methods to give400 grams (70%) of reduced compounds, B. P. 14 87-95. In an exactlysimilar manner there may be prepared:

and

CHr-CH:

H: H-CH O OCH:

Preparation of tetrahydroju'rfural formal A mixture of 204 gramstetrahydrofurfuryl alcohol (2 mols), 40 grams trioxymethylene (.45 mol),and 1 cc. conc. sulfuric acid are gently refluxedfor sixhours. After 15minutes all the paraformaldehyde has gone into solution. The reaction isallowed to stand overnight at room temperature and then neutralized withexcess sodium carbonate, filtered and'distilled. B. P. ISO-165; refr.index 1.4583 at 24; sp. gr. 1.075 at 24".

Our invention will be more readily understood by reference to thefollowing examples in which typical applications of the invention areset forth.

Example I. -A 20% solution of cellulose acetate in acetone in which isincorporated i-25% by weight of the cellulose acetate oftetrahydrofurfural glycol is extruded through fine orifices into anevaporative atmosphere. The filaments thus produced are wound or twistedand wound. Yarns produced from filaments thus prepared are pliable andsuitable for knitting.

Example II.-Yarn composed of cellulose acetate and designed for knittingpurposes is treated by applying thereto tetrahydrofurfural by means ofan applicator roll. The amount of the conditioning liquid may run from4-25% by weight of the yarn. If the yarn is intended for weaving, thesame procedure may be followed except that the amount of theconditioning agent added to the yarn is about 1-5%.

Example III .A conditioning liquid is made up by mixing the followingingredients in the indicated proportionsz' Ditetrahydrofurfuryl acetal70 parts ([lHr-CH: 1 (CH: HCHzO)=CH-CH:

0 g I Olive oil 30 parts This composition is applied to a celluloseacetate yarn intended for knitting in an amount representing 4-25% byweightof the untreated yarn. The filaments or fibers thus treated arequite soft and pliable and give excellent results in textile operations,especially knitting.

Other examples of yarn conditioning compositions which may be applied tovarious types of yarn, particularly cellulose acetate, cellulose acetatepropionate, and similar cellulose organic derivative yarns in accordancewith our invention and which render such yarns soft and pliable andwell-adapted for various textile operations, particularly knitting, arethe following:

Dltetrahydrofurfuryl p methoxyethylal '70 parts Blown neats-ioot oil 30parts Example VII Per cent Tetrahydrofurfural glycol '10 Light mineraloil 30 Example VIII Per cent Tetrahydrofurfuryl trimethylene glycol 50Sperm oil o I 50 o EzampleIX' Ber cent Ditetrahydrofurfuryl acetal 70Blown sperm oil 30 Example)! Parts 'Ditetrahydrofurfuryl formaL 30 Blownteaseed oil 70 Example XI Parts Tetrahydrofurfural diethylene glycol 40oar-on, oo,H4 Cg: HCH\ /O O 0-0234 Teaseed oil 60 Example XII Parts Ditetrahydrofurfurylfurfural 60 Blown neats-foot oil 40 As will beapparent from the above examples and description, the conditioningagents of our invention may be applied by a wide .variety of methods.For example, we may employ the agent as an ingredient of the spinningdope from which the filaments. are formed, the amount of the agent soemployed depending upon a number of factors, such as the particularcellulose deriva-- tive used in making the yarn, the solvent or solventcombination used in making up the spinning solution, and the degree ofsoftness or pliability desired in the yarn, etc.

If the conditioning agent is to be applied to the yarn after spinning,this may be done by bringing the yarn in contact with a wick, roll, orfelt wet therewith or the liquid may be applied by immersion, spray, orotherwise. The particular point at which the liquid is applied may vary.It may, for example, be applied to the yarn inside or outside thespinning cabinet, between the guide and godet roll, between the godet orother roll or guide and the-point of winding and/0r twisting. In somecases, the liquid may even be applied to the yarn after winding ontocones, spools, bobbins, or' the like or by the so-called bobbin tobobbin method. In the case of staple fiber manufacture, the liquid maybe applied to the yarn prior to, or after cutting into staple lengths.

The amount of the agent so employed will vary widely depending upon theresults desired, the specific nature of the material to which the agentis applied, the use to which the yarn is eventually to be put and otherfactors. For example, in a given case where a cellulose organic acidester yarn such as a yarn composed of cellulose'acetate, is intended forknitting, about 4 to 25% or more by weight, based onthe weight of thedry yarn, may be satisfactory, while if the yarn is intended forweaving. the amount mayvary-between about 1 and 5%.

Although i in the above examples we have C.

. fer-red primarily to yarn trgating g pmpositions containing only thecondition n wt and an.

vents emulsifying agents, blending; agents and the like, may be addedwithin. the scope of our invention. Likewise, various dyes: or othercoloring matter may be included in it'is desired to permanently orfugitively-tint or dye the material undergoing treatment.

Although we have found it convenient to illustrate our invention byreference tocompositions containing specific percentages of the variousingredients, these percentages may vary widely depending upon theparticular purpose for which the composition is intended. For example,if it is desired to control the solvent or softening action of theconditioning agent, the-amount of the agent may be adjusted as, forexample, by reducing the amount of the agent and correspondinglyincreasing the amount of oil or other ingredient.

While we have described our invention with particular reference to thetreatment of yarns composed of organic derivatives of cellulose such ascellulose acetate, the conditioning agents and formulas described hereinare applicable to the conditioning of many other types of cellulosederivative yarns such as those composed of or containingcellulose'propionate, cellulose butyrate, cellulose acetate propionate,cellulose acetate butyrate, ethyl cellulose, methyl cellulose, benzylcellulose and others, as well as to the conditioning of silk, wool,cotton, viscose and other natural or artificial materials.

The term ".varn as used herein and in the claims is to be understood asincluding a single filament, a plurality of filaments associated intothe form of a thread, either of high or low twist, single or multiplethreads associated or twisted together, composite threads composed of amixture of natural and artificial filaments or a com.- posite threadformed by twisting together individual strands of natural or artificialmaterials, as well as cut staple fibers produced from natural and/orartificial filaments or threads and spun yarn produced from such staplefibers.

As. indicated above, the yarn conditioning agents of'our invention areexceptionally good solvents for a wide variety of mineral, blown andunblown, drying and semi-drying animal and vegetable oils such ascottonseed, olive, castor, neat's-foot, sperm and other oils. Thisenables them to be used with any of such oils in making up a variety ofyarn treating formulas of varying composition.

The yarn conditioning method and compositions of our invention possessmany outstanding advantages. The fundamental and outstandincharacteristics of the agents employed in accordance with the inventionis their ability to soften yarns, especially those composed of orcontaining organic derivatives of cellulose such as cellulose acetateand render them soft and pliable and amenable to various textileoperations, especially operations such as those involved in weaving andknitting where complicated designs or stitches areemployed, without toodrastic an action onxthe yarn materlaL' Another outstandingcharacteristic of these compounds is their exceptional solvent power fora wide variety of mineral, animal and vegetable oils and their abilityto act ,as lubricating assistants in conjunction with these oils whenapplied to such yarns.

beg readily removed from yarns and fabrics, by means of -the usualaqueous-scour. baths. By em- In 7 addition, due to their solubility inwater, they may ploying the yarn conditioning agmrflsmethod 16 1 of ourinvention as herein described, one is enabled to obtain highlysatisfactory results in the manufacture of yarns and woven fabrics andthe production from these yarns of closely knit fabrics free fromdefects such as pin holes, stitch ing the formulas:

( nn-0H, /R' on, ell-ciao -c where R and R is a substituent selectedfrom the group consisting of hydrogen, alkoxy and alkyl andtetrahydrofurfuryl.

2. The process of conditioning yarn composed of or containing organicderivatives of cellulose to render it more amenable to textileoperations including knitting, weaving, spinning and the like and whichcomprises applying thereto a lubricating and softening compositioncontaining as its essential lubricating and softening compound an acetalselected from the group consisting of acetals having the formulas:

CH:CH:

CHrC H: R I A CE! E-CHiO C\ where R and R is a substituent selected fromthe group consisting of hydrogen, alkoxy and alkyl andtetrahydrofurfuryl.

3. The process of conditioning yarn composed and of or containingcellulose acetate to render'lt more amenable to textile operationsincluding knitting, weaving, spinning and the like, which comprisesapplying thereto a lubricating and softening compomtion containing asits essential lubricating and softening component anacetal selected fromthe group consisting of. acetals having the formulas:

CHr-C HI /0\ where R and R is asubstituent selected from the groupconsisting of hydrogen, elbow and alkyl and tetrahydrofurfuryl. I

4. The process of conditioning yarn composed of or containing celluloseacetate to render it more amenable to textile operations includingknitting, weaving, spinning and the like, which comprises applyingthereto a lubricating and softening composition containing as itsessential lubricating and softening component an acetal selected fromthe group consisting of acetals having the formulas: 7

, and

where R and R is a substituent selected from the group consisting ofhydrogen, alkoxy and alkyl and tetrahydrofurfuryl and a textilelubricant.

5. The process of conditioning yarn composed of or containing celluloseacetate to render it more amenable to textile operations includingknitting, weaving, spinning and the like, which comprises applyingthereto a lubricating and softening composition containing as itsessential lubricating and softening component the cellulose acetate oftetrahydrofurfural glycol.

6. The process of conditioning yarn composed of or containing celluloseacetate to render it more amenable to textile operations includingknitting, weaving, spinning, and the like, which comprises applyingthereto a lubricating and softening composition containing as itsessential lubricating and softening component ditetrahydrofurfurylacetal '7. The process of conditioning yarn composed of or containingcellulose acetate to render it more amenable to textile operationsincluding knitting, weaving, spinning and the like, which comprisesapplying thereto a lubricating and softening composition containing asits essential lubricating and softening component dltetrahydrofurfuryltetrahydrofurfural.

8. A conditioning agent for rendering yarns more amenable to textileoperations including knitting, weaving, spinning, and the like whichcomprises an acetal selected from the group consisting of acetals havingthe formulas:

H: HCH (cHa) h I, a, m.

and

tives of cellulose more amenable to textile operations includingknitting, weaving, spinning, and

the like which comprises an acetal selected from the group consistingofacetals having the general formulas:

' cam-on, 0

1 enon 0111) I, a, m.

and

where R and R is a substituent selected from the group consisting ofhydrogen, alkoxy and alkyl and tetrahydrofurfuryi and atextilelubricating oil.

10. A conditioning agent for rendering yarns composed 01' or containingcellulose acetate more amenable to textile operations includingknitting, weaving, spinning and the like containing the celluloseacetate of tetrahydrofurfural glycol.

11. A conditioning agent for rendering textile yarns composed of orcontaining cellulose acetate more amenable to textile operationsincluding knitting, weaw'ng, spinning and the like containingditetrahydrofurfuryl acetal.

12.' A conditioning agent for rendering textile yarns composed of orcontaining cellulose acetate more amenable to textile operationsincluding knitting, weaving, spinning and the like-containingditetrahydrofurfuryl tetrahydrofuriural.

l3. Textile yarn amenable to textile operations including knitting,weaving, spinning and the like impregnated with a. lubricant containingan acetal selected from the group consisting of acetals having theformulas:

ens-on, o

. Hg CB-CH\, /[CH1)1, I, 8, etco o and where R and R. is a. substituentselected from the group consisting of hydrogen, alkoxy and alkyl andtetrahydroiurfuryl. j

14. Textile yarn composed of or containing organic derivatives ofcellulose amenable to textile operations including knitting, weaving,spin-- ning and the like, impregnated with a conditioning agentcomprising an acetal selected from the group consisting of acetalshaving the formulas:

where R and R, is a substituent selected from the group consisting vofhydrogen, alkoxy and alkyl and tctrahydroiuriuryl.

15. Textile yarn composed of or containing organic derivatives ofcellulose amenable to textile operations including knitting, weaving,spinning and the like, impregnated with a condition- Certificate ofCorrection Pmm N'o. 2,153,134.

. It is hereby certified that error appears numbered patent requiringcorrect1on as f claim 15, in the formula, for

I and JOSEPH DICKEY ET AL.

in the printed specification of the above Hows: Page 5, second column,line 5,

read

ing agent comprising an acetal selected from, the

group consisting of acetals having the general formulae: 1

on,-on, 0 (3H, Hr-Cfi )CHDmmmo o and where R and R is a substituentselected from the group consisting of hydrogen, alkoxy and alkyl andtetrahydrofurfuryl and a textile lubricant.

l6. Textile yarns composed oior containing cellulose acetate amenable totextile operations ditetrahydrofurfural acetal.

18. Textile yarns composed of or containing cellulose acetate amenableto textile operationsinoluding knitting, weaving, spinning and the like,impregnated with a lubricant comprising ditetrahydroiuriuryltetrahydrofurfural.

19. As new chemical compounds acetals selected from the group consistingof acetals hav- I ing the formulas:

CHr-CH| /0 Ha AIR-CH )CHahmm.

wherein R; and R is a substituent selected from the group consisting ofhydrogen, alkoxy, alkyl and tetrahydrofin'furyl.

20. .As anew chemical compound, the cellulose acetate ortetrahydroiuriural glycol.

21. As a new chemical compound, ditetrahy- 'drofuriuryl acetal.

22. As a new chemical compound, ditetrahydroiuriuryl tetrahydroiuriural.

JAMES G. MCNAILY. JOSEPH B. DICKEY.

April 4, 1939.

and that the said Letters Patent should be read with this correctiontherein that the same may conform to Signed and sealed this 27th day ofJune,

[amt] the record of the case in the Patent Ofiice.

A. D. 1939. I Henri, Van Arsdale "Acting Commissioner of Patents.

